WO2007086852A2 - Method for making a non-toxic dense material - Google Patents

Method for making a non-toxic dense material Download PDF

Info

Publication number
WO2007086852A2
WO2007086852A2 PCT/US2006/002826 US2006002826W WO2007086852A2 WO 2007086852 A2 WO2007086852 A2 WO 2007086852A2 US 2006002826 W US2006002826 W US 2006002826W WO 2007086852 A2 WO2007086852 A2 WO 2007086852A2
Authority
WO
Grant status
Application
Patent type
Prior art keywords
recited
composition
density
tungsten
material
Prior art date
Application number
PCT/US2006/002826
Other languages
French (fr)
Other versions
WO2007086852A3 (en )
Inventor
John Roger Peterson
Original Assignee
Caldera Engineering, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/04Making alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ
    • C22C32/0084Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B12/00Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material
    • F42B12/72Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material
    • F42B12/74Projectiles, missiles or mines characterised by the warhead, the intended effect, or the material characterised by the material of the core or solid body
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B7/00Shotgun ammunition
    • F42B7/02Cartridges, i.e. cases with propellant charge and missile
    • F42B7/04Cartridges, i.e. cases with propellant charge and missile of pellet type
    • F42B7/046Pellets or shot therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147Alloys characterised by their composition
    • H01F1/14708Fe-Ni based alloys

Abstract

A composition having high density and low toxicity suitable for use as a shotgun pellet, a bullet or armor piercing projectile and a method for manufacturing such composition is described. This material and product are developed to economically address the toxicity problems inherent in lead shot and bullets. This composition, in its present embodiment, is also suitable for use in any product requiring high-density and low toxicity. One present embodiment maintains the magnetic properties of the projectile if desired.

Description

METHOD FOR MAKING A NON-TOXIC DENSE MATERIAL

Field of the Invention

This invention relates to methods and compositions for making material useful as

shot, bullets and the like. More specifically, this invention relates to methods and

compositions, for making non-toxic dense material for use in shot, bullets, milling media,

wear media, blasting media, hard tools and the like.

Background of the Invention

A variety of materials and methods have been proposed or are in use as shotgun

shot and rifle or pistol bullets, hereinafter referred cumulatively as "shot." Because of its

toxic nature, lead has been banned or criticized for use as shot. Lead has been banned in

the United States and Canada for use in shotgun shells for hunting waterfowl. Lead has

also been banned on all U.S. Federal Refuges when hunting game animals or training dogs.

Generally, the reasons for the bans and criticism are that when waterfowl ingest pellets, the

lead is retained and ground up in the bird's gizzard and poisons the bird. The principle

substitute for lead is steel, but the density of steel is only about 7.9 grams/cc, as

compared to 1 1 .4 grams/cc for lead or 1 1 grams/cc for commonly used lead alloys.

Because of the lower density the effectiveness of steel is greatly diminished when

compared to lead. One advantage of steel is that it is ferromagnetic, making it easily

detectable by law enforcement with a simple hand held magnet. Several manufacturers

have announced that they are working on finding a substitute for lead. These include Federal's Iron-Tungsten or Tungsten, Environmental's and Remington's Hevishot, Kent's

Tungsten-Matrix and Bismuth shot, made by The Bismuth Cartridge Company.

Federal's Iron-Tungsten or Tungsten claims a density of about 10.4 grams/cc,

although it has been measured at closer to 10.2 grams/cc. Iron-Tungsten uses a powder

metallurgy method of making a pellet from tungsten, iron and/or ferro-tungsten powders.

The process is described in U.S. Patents 5,831 ,1 88, 5,527,376, 5,905,936, 5,71 3,981 and

6,270,549. The process involves pressing each individual pellet in a press with a binder of

some sort to hold the pellet together in the "green" state. The pressing operation leaves a

band on the pellet that must be removed. After a presintering operation, the pellet is then

typically ground or rolled to make it truer (more round) and to eliminate or minimize the

band. Firing the pellet at about 1 500 degrees C in hydrogen gas then follows to densify

and strengthen the pellet. Further treatment may well include additional grinding and/or

the application of a rust inhibitor. This method tends to be expensive due to the high

firing temperature, the individual pressing of pellets and the followed rounding steps. This

individual pressing of pellets further limits the pellets to larger sizes.

Environmental and Remington claim that Hevishot has a density of about 1 2

grams/cc. The process of making Hevishot is generally described in US Patent No.

6,270,549. Hevishot uses a process of making shot from molten metal similar to the

method used historically to make lead shot by dropping molten lead through a screen

inside a tower, as the lead falls it becomes round and is quenched in water. Because

Hevishot is generally made of an iron, tungsten, nickel and sometimes a manganese alloy it

melts at a much higher temperature, about 1637 degrees C, than lead which melts at about 327 degrees C. Therefore, the process is modified to accommodate the much higher

temperatures. The process modifications include dropping the molten metal through a

ceramic sieve and, in place of the shot tower, into a high velocity stream of air or gas which

helps break up the molten droplets of metal alloy and allows the surface tension to form

round or rounded droplets that are then quenched in water. Unfortunately, Hevishot does

not tend to be very round and frequently has two or more spheres attached to each other

of different sizes or can be hollowed out and tend not to be of uniform size.

Kent's Tungsten-Matrix is claimed to have a density of 10.8 grams/cc, but

depending on the shot size measured between 10.3 and 10.7 grams/cc. This shot,

described in U.S. Patent No. 6,216,598, uses tungsten powder held together by a polymer.

Tungsten powder is much more expensive than FeW (ferro-tungsten) powder. Because of

the polymer, the resulting shot is comparatively weak and can deform during the shooting

process. Also, the process typically requires that the pellets be formed individually be

pressing from a polymer sheet, filled with tungsten powder, with opposing rolls.

Bismuth has also been proposed. However, with a density of 9.8 grams/cc Bismuth,

although relatively easy to manufacture, can be excessively brittle, unless alloyed with tin

(Sn) in small amounts. Sn has a density of 7.3g/cc, so any addition of Sn lowers the

density of the alloy.

A number of other shot materials and processes have been proposed. Generally,

however, these prior techniques have not made use of carbon to increase the density of the

shot and to reduce the firing temperature required, and the associated energy and

production costs. Although these references may not actually qualify as "prior art," the reader is

referred to the following U.S. patent documents for general background material. Each of

these patents is hereby incorporated by reference in its entirety for the material contained

therein.

U.S. Patent No. 1 ,847,61 7 describes hard alloys that include the addition of

chromium and cobalt.

U.S. Patent No. 2,1 1 9,876 describes shot used primarily in shot shells designed for

target shooting and game hunting and in air rifles.

U.S. Patent No. 2,1 83,359 describes a method of manufacture of heavy metallic

material, composed of tungsten, nickel and copper.

U.S. Patent No. 3,372,021 describes a tungsten addition agent for use in the

manufacture of steel.

U.S. Patent No. 3,623,849 describes powder metallurgy products using sintered

refractory compound materials and the method for producing such materials.

U.S. Patent No. 3,952,657 describes a cartridge that includes a projectile, which is

inserted in a plastic shell receiving a propellant charge, and the cartridge is expelled out of

a barrel by propellant gases.

U.S. Patent No. 3,987,730 describes iron and lead-containing composite metal shot.

U.S. Patent No. 4,027,594 describes shot pellets that are formed from finely divided

powder adhered together in pellet form by a thermoplastic polymeric material

decomposable in the acid environment of the digestive tract of waterfowl. U.S. Patent No. 4,1 67,904 describes a shot compressor device for use in shotgun

cartridges.

U.S. Patent Nos. 4,200,456 and 4,297,1 33 describe a method and member for

adding a treating agent for molten metal.

U.S. Patent No. 4,292,877 describes an ammunition loader with hoppers for shot

and/or powder and a slideable bar for measuring.

U.S. Patent No. 4,316,414 describes a fuse apparatus that arms itself in flight and is

especially adapted for use in training shells.

U.S. Patent No. 4,714,023 describes a non-toxic wildlife shot pellet for shotgun

shells and the like that comprises a lead shot pellet with a coating of nickel-phosphorous

alloys.

U.S. Patent No. 4,754,684 describes a method and device for cutting a shotgun

shell for shooting in a shotgun.

U.S. Patent No. 4,784,690 describes a low-density tungsten alloy article and the

method for producing the article.

U.S. Patent No. 4,841 ,866 describes a tracer shotgun shell that includes an

improved tracer element and a single integral wad member.

U.S. Patent No. 4,854,240 describes a two-stage, shaped charge projectile having a

rear principal charge and a front secondary smaller charge with an initiator-fuse assembly.

U.S. Patent No. 4,856,408 describes a modification or replacement for shot and

powder loading systems having wad jammer tubes with telescopic loading funnels. U.S. Patent No. 4,949,644 describes non-toxic wildlife shot pellets for shotgun

shells that are formed from bismuth or bismuth alloy.

U.S. Patent No. 4,960,563 describes a process for the product of a heavy tungsten-

nickel-iron alloy.

U.S. Patent No. 5,279,787 describes a high-density projectile and the method of

making the same from a mixture of low density and high-density metal powders.

U.S. Patent No. 5,335,578 describes a retrofitting shell feeding attachment for

shotgun shell reloading machines.

U.S. Patent No. 5,399,187 describes a composite lead-free bullet, comprising a

heavy constituent selected from the group of tungsten, tungsten carbide, carballoy and

ferro-tungsten and a second binder constituent consisting of either a metal alloy or a

plastic blend.

U.S. Patent No. 5,442,989 describes a method of making the casing for frangible

armor piercing incendiary projectiles.

U.S. Patent No. 5,51 2,080 describes a Fe-based alloy powder adapted for sintering,

a Fe-based sintered alloy, and a process for producing the Fe-based sintered alloy.

U.S. Patent No. 5,527,376 describes a shot pellet or small arms projectile that

comprises 40-60% by weight of tungsten and 60-40% by weight of iron formed by

sintering tungsten containing powders.

U.S. Patent No. 5,623,1 1 8 describes a shot shell wad that may comprise a powder

cup and a shot cup connected by first and second shot cup support members.

U.S. Patent No. 5,666,634 describes alloy steel powders for sintered bodies. U.S. Patent No. 5,71 3,981 describes a high specific gravity, lead free shot shell

pellets that are produced by preparing an iron-tungsten alloy, melting the alloy, pouring

the alloy and allowing the alloy to fall by gravity through a gaseous medium to form drops.

U.S. Patent No. 5,714,573 describes a melt-processable lactide polymer

composition, process for manufacturing these compositions and articles made from these

compositions.

U.S. Patent No. 5,719,352 describes a low toxicity shot or pellets for shotgun

cartridges or the like that comprises finely divided molybdenum and tungsten particles in a

polymer matrix.

U.S. Patent No. 5,728,349 describes a material primarily for sport shooting

ammunition, both pellet ammunition and ball ammunition, including at least the materials

zinc and bismuth.

U.S. Patent No. 5,760,331 describes a projectile made by combining two different

metals in proportions calculated to achieve a desired density, without using lead.

U.S. Patent No. 5,814,759 describes a composite lead-free bullet that comprises a

heavy constituent selected from the group of tungsten, tungsten carbide, carballoy and

ferro-tungsten and a second binder constituent consisting of either a metal alloy or a

plastic blend.

U.S. Patent No. 5,831 ,1 88 describes methods of making high specific gravity

shotgun shot and small arms projectiles from melts containing primarily tungsten and iron.

U.S. Patent No. 5,861 ,572 describes a universal shotgun shell wad that may be used

to assemble a variety of shotgun shells with a wide variety of shot and powder loadings. U.S. Patent No. 5,870,989 describes an abrasion resistant valve seat made of

sintered alloy for internal combustion engines.

U.S. Patent No. 5,874,689 describes a one piece shot cup designed especially for

use in protecting the bore of a shotgun barrel.

U.S. Patent No. 5,905,936 describes generally rough sphere-shaped work pieces

made of fragile material that are ground into more uniform spheres.

U.S. Patent No. 5,91 3,256 describes a non-lead environmentally safe projectile and

explosive container.

U.S. Patent No. 5,922,832 describes melt-processable lactidue polymer

compositions.

U.S. Patent No. 5,932,828 describes a reloader with snap-in tools.

U.S. Patent No. 5,963,776 describes a projectile, such as a bullet, made by

combining two different metals in proportions calculated to achieve a desired density,

without using lead.

U.S. Patent No. 5,970,878 describes a combination of shot sleeve and a shot cup

base form a universal shot wad that precisely fixes an adjustable volume.

U.S. Patent No. 5,997,805 describes a manufacturing method for the production of

high density, high carbon, and sintered powder metal steels.

U.S. Patent No. 6,048,379 describes a high-density composite material that may act

as a replacement for lead in applications where the high density of lead is important, but

where the toxicity of lead is undesirable.

U.S. Patent No. 6,092,467 describes a flare apparatus that includes a shell base. U.S. Patent No. 6,102,820 describes an auto-tensioner that inhibits the generation

of heat in an insert bearing made of a synthetic resin.

U.S. Patent No. 6,1 1 2,669 describes a lead-free projectile made from a composition

containing about 5-25% by weight of tungsten and more than about 97% by weight

tungsten plus iron.

U.S. Patent No. 6,1 28,846 describes an improved shotgun choke tube.

U.S. Patent No. 6,1 39,658 describes a metal matrix alloy that comprises carbon,

titanium and a matrix material.

U.S. Patent Nos. 6,149,705 and US 6,1 74,494 Bl describe non-lead,

environmentally safe projectiles and a method for making the same.

U.S. Patent No. 6,1 58,351 describes a ferromagnetic bullet that is lead free.

U.S. Patent No. 6,1 59,226 describes a process for producing a sintered powder

metal body.

U.S. Patent No. US 6,1 93,927 Bl describes a high density forming process with ferro

alloy and prealloy.

U.S. Patent No. US 6,202,561 Bl describes a shot shell that is comprised of shot

pellets of different densities and materials.

U.S. Patent No. US 6,209,180 Bl describes a composite shot for shot shells that

includes a ferrous metal core and a non-toxic coating having a density greater than lead.

U.S. Patent No. US 6,216,598 Bl describes shot for shotgun cartridges made from

finely divided particles of dense metal such as a mixture of tungsten and molybdenum,

bound by a matrix. U.S. Patent No. US 6,263,797 Bl describes a flare apparatus that includes a shell

case.

U.S. Patent No. US 6,270,549 Bl describes a ductile, high-density, non-toxic W-Ni-

Mn-Fe alloy compositions and methods of manufacture.

U.S. Patent No. US 6,358,298 Bl describes an iron-graphite composite powder

having a microstructure that comprises carbon clusters embedded in a ferrous matrix.

U.S. Patent No. US 6,439,1 24 Bl describes a lead-free projectile suitable for use as

a bullet to be fired from a pistol or rifle or as a slug to be fired from a shotgun.

U.S. Patent No. US 6,475,262 Bl describes a method of forming a component by

sintering an iron-based powder mixture.

U.S. Patent No. US 6,495,631 Bl describes a melt-processable lactide polymer

compositions, processes for manufacturing these compositions, and articles made from

these compositions.

U.S. Patent No. US 6,514,307 B2 describes a sintered iron-based powder metal

body with outstanding lower re-compacting load and having a high density and a method

of manufacturing an iron-based sintered component.

U.S. Patent No. US 6,51 7,774 Bl describes a high-density composite material that

may act as a replacement for lead in applications where the high density of lead is

important, but where the toxicity of lead is undesirable.

U.S. Patent No. US 6,527,880 B2 describes ductile medium and high density, non¬

toxic shot and other articles and a method for producing the same. U.S. Patent No. US 6,533,836 B2 describes an iron-based mixed powder for use in

powder metallurgy and die filling.

U.S. Patent No. US 6,536,352 Bl describes a frangible bullet comprising powder

particles of one metal bonded together by another metal wherein the metals have

substantially different melting points or an alloying metal is diffused between the metal

particles are manufactured by compacting the metal particles and heating under conditions

to create brittle bonds.

U.S. Patent No. US 6,537,489 B2 describes high-density products and method for

the preparation thereof.

U.S. Patent No. US 6,551 ,375 B2 describes ammunition using non-toxic metals and

binders.

Summary of the Invention

It is desirable to provide a method for producing non-toxic materials, which can be

used for shot and/or bullets, which are more dense than steel, bismuth or lead. It is

particularly desirable to provide an economical method for producing such non-toxic

materials.

Accordingly, it is an object of one embodiment of this invention to provide a

method for the manufacture of a dense material that is non-toxic.

It is another object of one embodiment of this invention to provide a method for the

manufacture of non-toxic material having a density of 9 to 1 1.8 g/cc and in some

embodiments even higher, up to and including densities of as much as 1 5 g/cc. Another object of one embodiment of this invention is to provide a method for the

manufacture of a more dense than lead material that is economically produced.

A still further object of one embodiment of this invention is to provide a method for

the manufacture of a more dense than lead material that has a relatively low sintering

temperature.

It is a further object of one embodiment of this invention to provide a method for

the manufacture of a more dense than lead material that uses relatively less expensive

materials.

It is a still further object of one embodiment of this invention to provide a method

for the manufacture of a more dense than lead material that is compatible with a wide

range of pellet sizes.

Another object of one embodiment of this invention is to provide a method for the

manufacture of a more dense than lead material that does not necessarily require grinding

or shaping, although grinding and shaping may be useful, but not necessary, in some

applications.

A further object of one embodiment of this invention is to provide a method for the

manufacture of a dense non-toxic material, which in some embodiments is provided with

an uneven dimpled surface.

A still further object of one embodiment of this invention is to provide a method for

the manufacture of a dense non-toxic material that includes sintering a different density

material such as tungsten powder to prevent sticking of the material to itself. Another object of one embodiment of this invention is to provide a method for the

manufacture of a dense non-toxic material that uses carbon as a sintering aid.

It is an object of one embodiment of this invention to provide a method for the

manufacturing of a dense non-toxic material that, in some embodiments, uses sintering in

tungsten powder to increase the density by tungsten incorporated into the surface and

alter the surface characteristics of the material.

It is another object of one embodiment of this invention to provide a method for the

manufacturing of a dense non-toxic material that, in some embodiments, employs

sintering in SiC, tungsten, ferro niobium and/or tungsten-carbide powder of a large mesh

size to prevent sticking of the pellets together during sintering.

It is a further object of one embodiment of this invention to provide a method for

the manufacturing of a dense non-toxic material that, in some embodiments, includes

Boron Nitride (BN) powder or spray to prevent sticking.

It is a still further object of one embodiment of this invention to provide a method

for the manufacturing of a dense non-toxic material that, in some embodiments, includes

non-wetting, high melting point material to prevent or reduce sticking of the resulting

pellets.

Another object of one embodiment of this invention is to provide a method for the

manufacturing of dense non-toxic material that, in some embodiments, lowers the

sintering temperature of FeW by the addition of a much higher melting temperature

material. A further object of one embodiment of this invention is to provide a method for the

manufacturing of dense non-toxic material that, in some embodiments, provides for the

varying of the strength and frangibility of the resulting material by varying the time and

temperature of the sintering stage as well as the composition.

A still further object of one embodiment of this invention is to provide a method for

the manufacturing of dense non-toxic material that, in some embodiments, provides the

proper strength and frangibility to milling media made from these compositions.

Another object of one embodiment of this invention; is to provide a method for the

manufacture of a dense non-toxic material that does not require compression or pressure

to form into a generally round shape.

It is another object of one embodiment of this invention to provide a method for the

manufacture of a dense non-toxic material that is useful in the manufacture of hard tools.

It is a further object of some embodiments of this invention to provide a method for

the manufacture of dense non-toxic material that retains magnetic properties.

A still further object of some embodiments of this invention is to provide a method

for the manufacture of shot of varying sizes with "tailored" densities to enhance the

trajectory control of the shot pellets.

Additional objects, advantages and other novel features of this invention will be set

forth in part in the description that follows and in part will be apparent to those skilled in

the art upon examination of the following or may be learned with the practice of the

invention. The objects and advantages of this invention may be realized and attained by

means of the instrumentalities and combinations particularly pointed out in the appended claims. Still other objects of the present invention will become readily apparent to those

skilled in the art from the following description wherein there is shown and described

present preferred embodiments of the invention, simply by way of illustration of the best

modes currently known to carry out this invention. As it will be realized, this invention is

capable of other different embodiments, and its several steps, details, and specific

components, dimensions and materials, are capable of modification in various aspects

without departing from the invention. Accordingly, the drawings and descriptions should

be regarded as illustrative in nature and not as restrictive.

Brief Description of the Drawings

The accompanying drawings incorporated in and forming a part of the specification,

illustrate embodiments of the present invention. Some, although not all, alternative

embodiments are described in the following description.

In the drawings:

Figure 1 is a flow chart of the present steps of the method of this invention.

Reference will now be made in detail to the present preferred embodiments of the

invention, examples of which are illustrated in the accompanying drawings.

Detailed Description

This invention is a material with a density adapted to be less than, equal to, or

greater than lead as desired for the particular use, but without the toxicity of lead, which is

appropriate for use as shotgun shot, bullets and the like, and the method of making such material. While the components of the present embodiment of this invention include

tungsten (W), iron (Fe) and carbon (C) along with a binder (which may typically be Acrawax,

Polyvinyl Alcohol (PVA), or Paraffin), a wide variety of alternative materials and/or specific

configurations of the materials, some of which are detailed and described in the following

description, can be substituted without departing from the concept of this invention.

Alternative binders include, but are not limited to: bees wax; oils including oil from light oil

to tar; organic binding materials including sea weed, sugars, molasses, corn syrup, maple

syrup, refiners syrups and the like; flour from wheat, rice, potatoes, corn and the like;

cheeses; gums; wood dust including saw dust, shavings, fibers and the like; cotton;

synthetic fiber; rubbers; cements; starches; ductile inorganic materials including metals

such as Al, Sn, Cu, Fe, Ni, Nb, V, Ti, clays, cements; silicon based materials including

silicone oils, waxes and greases; soaps including dry soap, liquid soap and stearates; and

other like materials that have the ability to help powders to stay together, even for a short

time or even just marginally, can be used as a binder. The components and the method of

manufacture are designed to minimize cost.

This invention specifically addresses the problem of using toxic materials, such as

lead, in hunting or likewise in a manner which tends to leave toxic materials in the

environment in a manner which can adversely affect the health of waterfowl and other

animals, ground water and the like. Because this invention uses economical materials,

generally lower heating temperatures and shorter heating time periods, and produces a

product in a pelletized form, without the requirement of pressing, machining or selecting

which can greatly increase the ultimate cost of the produced product, this invention directly addresses the need for an economically viable toxic-free solution for shot, bullets and the

like. The density of the material used in a shot and bullet product is directly related to the

effectiveness (range, predictability and take-down power) of the product. The greater the

density of the bullet material, the more effective the shot or bullet. Because rifle barrels

have a twist designed for lead bullets, it can be desirable to provide a high density core to

a non lead bullet, which is designed to bring the total density of the bullet to

approximately that of a lead bullet, thereby reducing or eliminating the need for

modification of the bullet cross-section or in the twist of the barrel to maintain bullet

accuracy when fired. The product of this invention meets these needs by using a tungsten

compound in combination with typically a carbon source mixed and formed in a manner

appropriate to facilitate the above desired product features. In the present embodiment

FeW (ferrotungsten) powder and graphite (carbon) is used to reach densities at about 1 1 .8

g/cc at processing temperatures at about 1 1 500C maintained typically for less than about

fifteen minutes. Throughout this description FeW is defined by the applicant to mean any

iron tungsten alloy in any suitable proportion. Variations, both higher and lower, in density

of the product are achieved with alternative temperatures, compositions and heating

periods, and therefore produce variations in frangibility and strength. Typically and

presently preferably the processing of the method of this invention is performed in a

Hydrogen, Argon or otherwise protective atmosphere.

Carbide compositions in this invention can be produced from ferroalloys by

attrition, the result then blended with carbon and fired at temperatures lower than those

necessary for forming carbides of the primary metal. Examples of such carbide compositions include, but are not necessarily limited to, FeW, FeTi, FeCr and other

ferroalloys that are suitable for alloying with steel and/or other alloys that contain iron and

carbon. Cutting tools that contain carbides, such as those made by cementing carbides

together with cobalt, nickel or iron can also benefit from the addition of carbided or

carburized ferroalloys. The carbiding or carburizing of the master ferroalloy, before the

addition of other alloys or cemented carbide tools, can provide an accurate method of

controlling the ratios of carbon and of the alloy additive. This control can be helpful in

maintaining the desired properties of the final product.

During the development of this invention the inventor determined that a very dense

compact can be made by sintering Nickel (Ni) and Manganese (Mn) with Tungsten powder

(W) at temperatures below 12000C. In some instances and embodiments densities greater

than 14 g/cc have been achieved. Using a combination of Ni, Mn, W and FeW densities in

excess of 12.5 g/cc have been achieved. NiMn alloys have particular advantages in this

process for making dense non-toxic material, including: Ni and Mn together form a low

melting eutectic, at about 10300C to 1 0400C with about 40-60% Ni in the NiMn alloy. Ni

melts at about 1 453°C and Mn at about 1 244 0C so either element alone does not sinter at

the low temperature of the eutectic. By varying the quantities of Ni and Mn the hardness of

the alloy is also varied, from too soft to measure to a value in the 80's on the Rockwell A

scale. In other words, the ratio between the amounts of Ni and Mn in the alloy can affect

the hardness from softer than many steels to as hard as some softer carbides. The range

of density achieved in the composition can also be adjusted by selecting the amounts of Ni

and Mn used. Using the NiMn sintering agent permits parts to be formed mechanically or machined to a final shape or dimension with standard metalworking techniques, i.e.,

pressing, rolling, cutting and the like. FeW-C parts when used as an alternative, typically

require grinding and other processes necessary for hard and brittle materials. Since NiMn

acts to hold the other materials in the composition, hardness, toughness, formability and

even the magnetic properties can be regulated by the way in which the powders are

assembled and sintered. For example, the FeW-C composition is non-magnetic and the

FeW, W and NiMn composites are also non-magnetic if the particle sizes in the powders are

kept small. However, when larger FeW particles are used the magnetic properties of the

large particles is retained, so long as the particles are merely held together and are not

allowed to react with the other constituents. Therefore, a non-magnetic or a magnetic

product can be produced from either the NiMn, FeW, W, or FeW-C composition. The NiMn-

W composition will not yield a magnetic product.

For some applications it is desirable to have magnetic properties in the product of

the process of this invention. One of these applications is the use of the product as shot in

shotshells for hunting waterfowl. It is probable that the components of the material of the

various present embodiments of this invention are sufficiently non-toxic to be used as shot

in shotshells as non-toxic shot. One of the common qualities of non-toxic shot is that it

may be easily determined in the field, by non-destructive and non-invasive techniques,

that the shot is non-toxic. A simple means that has been developed to make this

determination is the use of a magnet. Steel, a common non-toxic shot and some other

non-toxic shot have been demonstrated to be magnetic. Naturally, the magnetic properties of nearly any product can be altered by such means as coating the product with

a magnetic coating, such as BiMn, AlCuMn, which is both magnetic and non-toxic.

An alternative method of providing magnetic properties to the product is in the

method of manufacture. For example, Tungsten (W); Manganese (Mn); Carbon (C); Nickel-

Manganese (NiMn); and Iron-Tungsten-Carbide (FeWC) are all non-magnetic, while Iron-

Tungsten (FeW) and Iron (Fe) and Nickel (Ni) are all magnetic. When FeW is reacted with C,

the FeW ceases to be magnetic. Similarly, when Ni reacts with Mn it is no longer magnetic

above 30 to 40% Mn. If an alloy of Ni and Mn is used where the Ni is about 60% or more

the alloy will be magnetic and this magnetism will be retained in the final product. Any of

the products of this present invention can be made magnetic by not reacting the magnetic

component, that is, by using particles of FeW or Ni that are large enough so that although

they are part of the composition, then do not completely react and therefore retain their

magnetic qualities. By carefully choosing the desired particle size of the FeW and/or Ni, a

degree of magnetism can be retained in or can be removed from the final product. The

density of FeW is high so there is generally no sacrifice of overall product density when FeW

is used as the chosen material for magnetism, and in fact the use of FeW can enhance or

increase the overall density of the resulting product. While coatings may decrease to some

degree the overall density of the product, the use of FeW or other similar material that is at

least as dense, than the desired final product, does not tend to reduce the final product's

density. Other large particle magnetic materials, that do not tend to be changed by the

sintering steps, such as Fe, Ni and the like, can also be used to provide magnetism. The following is a brief summary of various elements and compounds that the

inventor has determined can be used in various ways and with a variety of results in the

process and product of this invention. This list is not intended to be exhaustive but rather

only to be exemplary of the wide variety of materials that may be employed in this

invention.

Nickel (Ni) can be applied by electrolysis and is commonly known and used in this

manner although electrolysis may not necessarily be the best way to apply Ni to shot to

magnetize the shot. Another alternative and probably better way of applying Ni is to place

the shot in a rotating mill with soft Ni powder such as Ni 1 23 and rotate the mill until the

Ni powder covers and adheres to the surface of the shot. This method of applying Ni

works equally well for applying Ni to any rough or cylindrical surface for which applying Ni

to the surface is desirable. The present product will accept Ni coating in this way and thus

provide the desired magnetic qualities required for detection of non-toxic shot in the field

with a simple magnet. Ni may also be coated on the shot by applying a slurry of Ni powder

and then drying and sintering at a temperature below the point where the Ni would

combine with the substrate to lose its magnetic property, but simply sintering to the

surface thereby retaining the magnetic qualities.

Bismuth-Manganese (BiMn) can be used as both a coating and as an inherent

material. As a coating the Bi is typically added with a low temperature dip after the product

is finished. Although Bi is not magnetic itself, it will tend to combine with the Mn in the

product for the requisite alloy. Testing has been performed and has determined that BiMn

alloys in the range of 1 part Bi and 3 parts Mn to 3 parts Bi and 1 part Mn produces a magnetic part, therefore close control of the composition is not generally necessary to

assure that the product retains magnetic qualities. Bi has a low melting point of about

2710C, which facilitates the application of the Bi to the product. Simply dipping the

product in melted Bi and/or reheating can be done relatively easily. Bi also provides some

corrosion protection, even though the product itself is generally quite corrosion resistant.

Surface coatings of BiMn can be applied in much the same manner as Ni powder if the BiMn

is made into a powder first, then rolled and used as is or sintered onto the surface at lower

temperatures than are normally required in processing. BiMn can also be used inherent to

the product composition to sinter or "glue" the denser materials, such as FeW, W and the

like, together. This use of BiMn also facilitates the magnetic quality of the product. A

present drawback to the extensive use of Bi is its high cost. However, if the cost of Bi

decreases and availability increases, this could be an attractive ingredient for the product

composition. Since the alloy, BiMn, would typically be about 80% by weight Bi the cost of

the Bi could be driving factor in the determination of its use. The Mn content makes the

sintering to good strength more feasible than with just Bi alone and the Bi is not magnetic,

while the alloy BiMn is. BiMn also appears to wet to almost anything it contacts and

therefore can be a problem as a sintering agent, since it will tend to stick to nearly

everything.

Aluminimum-Copper-Manganese (AICuMn) is also a low melting point alloy and can

be applied to the product by dipping, spraying or other similar means to provide a coating

on the product. This alloy further has the advantage than Mn is already likely to be present

in the base material, so the Cu and Al can be the coating. Cu and Mn make a good combination for sintering and can be altered with a small amount of Al to provide the

desired magnetic properties. AICuMn can also be applied in much the same manner as

described in relation to Ni powder if made into a powder first, then rolled and used as it or

sintered onto the surface at lower temperatures than is typically required in standard

processing. The CuMn alloy does not provide as high a density as NiMn, but is sufficient

for most applications, such as shot, projectiles, fishing weights and the like.

Iron (Fe) and Chromium (Cr) can also be applied as a powder to the surface, either

with adhesive or sintered on to the product to provide the desired magnetic properties.

The amount of Fe and Cr that should be used depends on the desired magnetism and the

resulting density. Fe, steel, Ni, Cr and other magnetic materials can also be applied as

coatings, although for some with difficulty. Fe and steel are not corrosion resistant unless

they are in turn coated, as some steel shot presently is. Ni has been coated onto the final

product as a powder with separate steps, following the primary sintering, of coating with a

Ni powder, which has some kind of binder, such as sugar water, to attach the powder to

the sintered article, followed by another sintering step to sinter the Ni metallurgically. This

second sintering step can be eliminated if the binder is sufficiently strong to keep the Ni or

other magnetic material in place.

Copper-Manganese (CuMn), Manganese-Nickel (MnNi) and Copper-Nickel-

Manganese (CuNiMn) all have melting points below or well below 1 2000C, thus making

processes using these alloys into a relatively less expensive and more economical realm for

manufacturing. Other factors, such as the sintering-aid effect previously described as part

of the FeW-C mix can also be important in the effectiveness of this process. Mn has been found to provide this sintering-aid effect when it is included in the composition, such as in

CuMn, MnNi and CuMnNi alloys. Mn is also beneficial for not only lowering the melting

point of the composition but also for assisting the sintering step and densification,

whenever Mn is present and if the proportions of Mn is higher the effect is magnified. Cu

appears to have the opposite effect and when Cu is increased, the composition sintering-

aid effect is reduced, to the point where if Cu is the only component, sintering is minimal

or almost nonexistent even though the melting point of Cu is well below the processing

temperatures. No sintering-aid effect has been found for Ni, since the melting point of Ni

is well above the typical processing temperatures. Mn alone, among the studied elements,

melts well above the processing temperatures but aids sintering and densification, so that

the full benefit of Mn is made available at the process temperatures when Mn is alloyed

with other elements that lower the melting temperatures below 1 2000C, and typically much

below 1 2000C. Other elements that Mn alloys well with are Tin (Sn) and Zinc (Zn).

Tin-Zinc (SnZn) and Manganese-Tin-Zinc (MnSnZn) are alloys that have very low

melting points and are not easy to make into powders. Although powders may not always

be necessary at the low temperatures if wetting is good or excellent. SnZn does not wet as

well without the Mn, so small amounts of Mn are preferably added to the alloy for wetting

and sintering. 4% Mn added to the composition helps wetting at 1 2000C, but does not

typically increase the density values significantly because there was very little increase in

sintering. Greater amounts of Mn are desirable for increasing the sintering and has been

demonstrated with 10% Sn and 80% Mn compositions. Larger amounts of Mn can reduce the retained magnetism unless sintering temperatures, and sometimes densities, are

lowered or particle size of the magnetic materials are increased.

The following are some examples of compositions, processing temperatures and

atmospheres and resulting products of this invention. These examples are not intended to

be exhaustive but rather only present examples of various embodiments of the

composition of this invention. These examples are presented by showing the approximate

quantity of each major constituent, the firing (sintering) temperature, the atmosphere

preferred, the sintering time, the resulting hardness in Rockwell Hardness Units (RHA),

scale A, the product density, and whether the product is magnetic. For the approximate

quantity of the constituent the values provided have been rounded to the nearest

percentage. These percentages are not intended to imply that no other constituent

elements, alloys, compounds or compositions are included, rather they describe the

relative quantities of the major constituents pertinent to the objective of a non-toxic dense

material. Other various components may and generally are included in the final product as

trace elements or contaminants. Mesh sizes are provided where pertinent using standard

US sieve mesh sizes. With this tabular description additional comments and notes are

provided to give other specific information related to the particular embodiment.

Example 1 - An example of the use of Tin.

Ex# Sn Mn W FeW Firing Temp Atmos Time Dnsty Mag

1 -8.3 -1 6.6 -41 .7 -33.2 1 200 ° C Ar 1 hr 1 1 .5 slightly Example 2 - FeW powder is mixed with fine carbon powder (graphite)

Ex# FeW C Firing Temp Atmos Time Hardness Density Mag

2 -98.6 -1.4 1175°C H 15 m 67 11.7 no

High hardness is provided because of the carbides formed at the temperatures

where the sintering takes place, some WC can be formed in the reaction sintering as the

bond between the Fe and W is broken by C.

Examples 3-6 - Ni1 Mn and -100 to +400 mesh, in a ration of about 1 /2/4 with W

powder added as noted in each.

Ex# Ni Mn FeW W Firing Temp Atmos Time Hrd Dnsty Mag

3 -10 -20 -40 -30 1200°C Ar 15m 27±10 10.0 no

4 -8.3 -16.6 -33.2 -41.7 1200°C Ar 15m 41 ±18 10.9 no

5 -7.1 -14.2 -28.4 -50 1200°C Ar 15m 31 ±7 11.6 no

6 -6.3 -12.6 -25.2 -56.3 1200°C Ar 15m 45±5 11.9 no

These hardness ranges go from well below that which is accepted hardness for steel

shot and other "hard" shot to about the same as is found in such steel shot. The relatively

large variation in hardness in these examples shows the variation possible with a multiple

phase product. Examples 7-10 - Ni, Mn and -200 mesh FeW powder, in a ratio of about 1/2/4,

with W powder added as noted in each example.

Ex# Ni Mn FeW W Firing Temp Atmos Time Hrd Dnsty Mag

7 -10 -20 -40 -30 1200°C Ar 15m 46±6 10.6 no

8 -8.3 -16.6 -33.2 -41.7 1200°C Ar 15m 46±9 11.1 no

9 -7.1 -14.2 -28.4 -50 1200°C Ar 15m 47±3 11.7 no

10 -6.3 -12.6 -25.2 -56.3 1200°C Ar 15m 47±0 12.0 no

These examples are somewhat softer than that typically used in the market for

"hard" shot.

Example 11 - Ni, Mn and W powders used to make a dense sintered product. The

powders are mixed and fired.

Ex# Ni Mn W Firing Temp Atmos Time Hrd Dnsty Mag

11 -6.6 -15.4 -80.0 1200°C Ar 15m 53±2 14 no

The density of this example is very high compared to related product compositions.

The density can be varied by the addition of more or less of the lower density Ni and Mn, in

other manufacturing processes these types of higher densities typically require expensive,

hot pressing and/or high temperature manufacturing techniques (above 12000C) . The

particle sizes of the W powder can also be modified to control the hardness and density,

where the larger the W particle size, leads to lower hardness and increased density. The larger particle W powder also tends to lower the porosity both open and closed for the

resulting product.

Examples 12-15 - Examples of the effect of the particle size of W on hardness, the

finer the W particles, the harder the resulting product. In this table the tungsten size is

average particle size in μm.

Ex# Ni Mn FeW W/size Firing Temp Atmos Time Hrd Dnsty Mag

12 -5.5 -12.6 -25.2 -56.7/40 1200°C Ar 15m 41 ±3 12.3 no

13 -5.5 -12.6 -25.2 -56.7/20 1200°C Ar 15m 42±7 12.2 no

14 -5.5 -12.6 -25.2 -56.7/12 1200°C Ar 15m 48±8 12.4 no

15 -5.5 -12.6 -25.2 -56.7/6 1200°C Ar 15m 60±4 12.4 no

As can be seen in these examples (Examples 12-15) there is not much effect on the

hardness until the particle size approaches 12μm and finer, with a profound effect at 6μm

average particle size. Showing that hardness can be controlled, within a range, by the

particle size of W.

Examples 16-24 - Magnetic enhanced products.

It is possible, in various embodiments of this invention, to enhance or reduce

magnetic qualities of the resulting product by the use of careful selection of particle sizes

and the metals chosen as the sintering medium. Metals such as Mn and Ni or C in FeW-C composition, react with the FeW to cause the FeW to lose the ferromagnetic property that is

naturally possesses. Other metals, such as Cu, Zn and Sn can be used in sintering with a

reduced effect on the magnetic properties of the FeW or other magnetic additions because

of the reduced reaction with magnetic materials. For this reason Ni and Mn can be used to

sinter and obtain high densities with no magnetism if such is desired and can be mixed

with Cu, Sn and/or Zn to achieve the same results, although Cu appears to reduce the

sintering/densification and the resultant densities to some degree. However, if Cu, Sn and

Zn and their alloys are used the magnetic properties of the resulting product are largely

unaffected and their magnetism is retained. Since the NiMn alloy composition provides

higher densities, it can also be desirable to use NiMn as the sintering medium, and to

thereby retain the magnetic properties of the product. Hence, the magnetic properties of

the FeW or other magnetic material in the product mix can be retained even if the sintering

medium reacts with the magnetic material by using a particle size that does not react

completely but is still sintered densely. Among the several advantages of using a larger

particle size FeW are: (1 ) Since FeW is quite hard and not very friable it is much easier to

obtain a larger, particle size and therefore is therefore is generally less costly to grind to a

large size. (2) The density of FeW is about 1 3.9 g/cc and, if it is used in a larger size,

contributes to the overall density by the reduction of porosity or potential porosity. (3)

Larger particle sizes tend to reduce the average hardness of the product. This can be an

advantage for any use such as projectiles or shot where there is a concern for barrel wear

or scarring. (4) Lower temperature processing reduces the interaction of the sintering

medium with the magnetic component leaving more of the component unaltered and thereby contributing to the retention of magnetism in the product. These factors are

demonstrated by the following examples 16-24.

In Examples 16-18 the mesh size of the FeW is +200.

Ex# Ni Mn FeW W Firing Temp Atmos Time Dnsty Mag

16 -7.7 -20.5 -41.0 -30.8 1200°C Ar 15m 10.8 yes

17 -6.4 -17.0 -34.0 -42.6 1200°C Ar 15m 11.4 yes

18 -4.8 -12.7 -25.4 -57.1 1200°C Ar 15m 12.1 yes

The magnetic qualities of the product are proportional to the non-magnetic

components, namely, NiMn is non-magnetic, if the Ni is lower than 60%, as is W, so that

portion of unreacted FeW is the magnetic component, and the magnetism is therefore

reduced proportionally.

In Examples 19-22 the objective is to not retain any ferromagnetic properties. The

mesh size of the FeW is -200.

Ex# Ni Mn FeW W Firing Temp Atmos Time Hrd Dnsty Mag

19 -7.7 -20.5 -7.7 -30.8 1200°C Ar 15m 50 10.7 no

20 -6.4 -17.0 -20.5 -42.6 1200°C Ar 15m 50 11.5 no

21 -5.5 -14.5 -30.8 -50.9 1200°C Ar 15m 50 12.0 no

22 -4.8 -12.7 -41.0 -57.1 1200°C Ar 15m 50 12.4 no In Examples 23-24 are shown other examples for retaining magnetism to a higher

degree with larger ferromagnetic particles. The FeW particle sizes are from + 100 mesh to

-20 mesh.

Ex# Ni Mn FeW W Firing Temp Atmos Time Hrd Dnsty Mag

23 -8.3 -1 6.6 -33.3 -47.7 1200°C Ar 1 5m 47 1 1 .7 yes

24 -7.2 -14.2 -28.5 -50.0 1200°C Ar 1 5m 45 12.3 yes

Each of these examples (23 and 24) were highly ferromagnetic and would be easily

detected by a magnet in nondestructive field testing of a shotshell for magnetic shot.

Other tests with still larger FeW particle sizes, showed that the retained magnetism

increases with the particle size until the particles were too large and allowed open porosity.

The presently known optimal size for the FeW particles is found to be between greater than

200 mesh and less than 10 mesh, although mixtures of large mesh size particles can still

provide low porosity and high density. Where magnetism is desired with a porous

structure, this can be readily obtained with a large mesh sizes, even up to and exceeding

10 mesh.

Examples 25-32 demonstrate the use of CuMn. Cu was previously considered to be

eliminated from use because of known toxicity. More recent tests have shown that the

toxicity to waterfowl of Copper is dependent on the residence time in the gizzard and the

otherwise in the bird. Government approval has been granted to use Cu containing shot so tests have been conducted using CuMn, because of the low melting point of such alloys

and the ability of Mn to act as a sintering aid.

Ex# Cu Mn FeW W Firing Temp Atmos Time Mag

25 -20.0 -10.0 -40.0 -30.0 1200°C Ar 15m no

26 -16.0 -8.0 -32.0 -41.6 1200°C Ar 15m no

27 -14.0 -7.0 -28.0 -50.0 1200°C Ar 15m no

28 -13.0 -6.5 -26.0 -56.2 1200°C Ar 15m no

Only a small amount of sintering was observed with little or no shrinkage.

Ex# Cu Mn FeW W Firing Temp Atmos Time Dnsty Mag

29 -10.0 -20.0 -40.0 -30.0 1200°C Ar 15m 10.2 no

30 -8.3 -16.6 -33.2 -41.7 1200°C Ar 15m 10.8 no

31 -7.1 -14.2 -28.4 -50.0 1200°C Ar 15m 11.4 no

32 -6.3 -12.6 -25.2 -56.3 1200°C Ar 15m 11.8 no

Reversing the ratio of Cu and Mn increases the density, probably due to the higher

Mn or the lower Cu. The densities are lower than when Ni is used in place of Cu at the

same ratios even though Ni and Cu densities are quite close at 8.96 g/cc for Cu and 8.90

g/cc for Ni. Examples 33-36 shows examples CuSn as a sintering aid.

Ex# Cu Mn FeW W Firing Temp Atmos Time Dnsty Mag

33 -1 0.0 -20.0 -40.0 -30.0 750 ° C Ar l hr porous yes

34 -8.3 -1 6.6 -33.2 -41 .7 750 ° C Ar l hr porous yes

35 -7.1 -1 4.2 -28.4 -50.0 75O ° C Ar l hr porous yes

36 -6.3 -1 2.6 -25.2 -56.3 750 ° C Ar l hr porous yes

With no shrinkage this composition can be used to fire near net shape of the mold

used. This composition has application where no shrinkage is important and little or no

density increase from the formed part upon firing.

Example 37 is an example of SnI OZn sintering. This example is sintered at 1 200 °C

for 1 hour in Ar. Zinc is known to be especially toxic to waterfowl, so this example

composition may have application only in non-hunting uses, although the dwell time in the

digestion system for ingested shot may be short enough to make this a viable application,

especially with low levels of Zn in the alloy. This alloy has a very low melting point at

1 98.5 ° C and there are no intermetallics formed, which may harden the alloy more than the

initial introduction of Zn. This alloy did not wet the W and FeW component powders so no

sintering took place and the alloy is assumed to have limited effectiveness, unless a

wetting flux such as flux is applied. Fluxes are available for no lead solders, which this

alloy is similar to, and may work with the alloy. A Sn l OZn4Mn alloy was also used to see if

the Mn additive can solve the wetting problem in the SnI OZn alloy described above. The

result was that the wetting did occur but that no significant sintering occurred. The result for this composition was similar to that of CuSn, in that it can be used for making a solid

low strength piece at a near net forming shape.

Examples 38-43 are of the use of the alloy MnSn, which has a low melting point, as

does MnSnCu and MnZn.

Ex# Sn Mn Cu Zn FeW W Temp Atm Time Dnsty Mag

38 -8.3 -16.6 0 0 -33.3 -41.7 1200°C Ar lhr 1.5 some

39 -4.7 -16.6 -4.7 0 -33.3 -41.7 1200°C Ar lhr 11.0 yes

40 -4.3 -17.4 0 0 -34.8 -60.9 1200°C Ar lhr 11.4 some

41 -3.7 -14.8 0 0 -29.6 -51.8 1200°C Ar lhr 11.9 yes

42 0 -17.4 0 -4.3 -34.8 -60.9 1200°C Ar lhr porous no

43 0 -16.0 0 -4.0 0 -80.0 1200°C Ar lhr porous no

The magnetism in the samples with Sn and the additional magnetism in the sample

with Cu provides additional compositions of interest. Particular effects of several of these

low melting alloys have been observed. Cu, Sn and to a certain degree Zn, none of which

have much solubility in or reactivity with Fe or W, appear to inhibit sintering or

densification while many compositions containing Mn have densification enhanced and the

more Mn in the composition, the more sintering is provided, so long as the melting point

of the mixture or alloy is below the sintering temperature of 1200° C, chosen for the

economics of production. Examples 44-59 show the use of additional alloys for sintering dense materials.

Ex# Cu Mn W Temp Atm Time Dnsty

44 -33.3 -16.6 -50.0 1200°C Ar 15m 9.5

45 -22.2 -11.1 -66.6 1200°C Ar 15m 10.9

46 -16.6 -8.3 -75.0 1200°C Ar 15m 11.2

47 -13.3 -6.6 -80.0 1200°C Ar 15m 11.9

Examples 44-47 shows compositions with lower densities than are shown in

examples 48-51, but show that the selection of density is selectable by adjusting the

Cu/Mn ratio.

Ex# Cu Mn W Temp Atm Time Dnsty

48 -16.6 -33.3 -50.0 1200°C Ar 15m 10.2

49 -11.1 -22.2 -66.6 1200°C Ar 15m 11.9

50 -8.3 -16.6 -75.0 1200°C Ar 15m 12.3

51 -6.6 -13.3 -80.0 1200°C Ar 15m 13.2

Examples 52-55 show the use of CuMnW(FeW).

Ex# Cu Mn W FeW Temp Atm Time Dnsty

52 -10.0 -20.0 -30.0 -40.0 1200°C Ar 15m 10.2

53 -9.1 -18.2 -45.4 -36.4 1200°C Ar 15m 10.8

54 -7.7 -15.4 -53.8 -30.8 1200°C Ar 15m 11.4

55 -6.6 -13.2 -60.0 -26.6 1200°C Ar 15m 11.8

Examples 56-59 show the use of powders mixed and then fired.

Ex# Cu Mn Temp Atm Time Dnsty

56 -80.0 -20.0 1200°C Ar 15m 10.2

57 -66.6 -33.4 1200°C Ar 15m 10.8

58 -57.1 -42.9 1200°C Ar 15m 11.4

59 -50.0 -50.0 1200°C Ar 15m 11.8

These results are obtained even though Cu is more dense, 8.96 g/cc, than Mg at

7.43 g/cc. The alloys in these examples are less dense than the lighter of the two

components when mixed at a 50-50 weight percentage. This shows that when used as a

sintering alloy for W and W plus FeW, the higher Mn content, the less dense the resulting

metal and the higher the sintered density. This shows the "sintering aid" effect of the Mn,

since even thought the CuMn alloy is less dense with higher Mn sintered product with W is

denser. Examples 60-63 show compositions with Mn, Ni and Graphite (C) without W, only

FeW.

Ex# Mn Ni C FeW Temp Atm Time Dnsty Mag

60 -6.0 -1.9 -1.2 -82.7 1200°C H 15m 10.2 no

61 -5.9 -2.0 -1.4 -82.5 1200°C H 15m 10.8 no

62 -5.8 -2.1 -1.6 -82.3 1200°C H 15m 11.4 no

63 -5.9 -2.0 -1.8 -82.1 1200°C H 15m 11.8 no

This demonstrates the present most economical composition that still provides

corrosion resistance and a high density.

Example 64 shows a composition with the use of oxides of FeW.

Ex# Oxide C FeW Temp Atm Time Dnsty Mag

64 -17.2 -4.0 -78.7 1200°C H 15m 11.5 no

The use of oxides provides similar results to the mixes without oxides. This is

extremely important to the use of starting materials as they can be either FeW as a

compound or the burned oxides of FeW. The easiest way to reduce the particle size to a

good range for manufacture may be to "burn", or oxidize the FeW in air or oxygen at high

temperature and then screen and add the burned material to the process, either as the

total component or mixed with metallic FeW in the chosen proportions. The advantages

are lower cost materials and ease of production. Referring now specifically to figure 1 , which details the present steps of the

processing method of this invention. Carbon is loaded 101 for use in the composition. In

some present preferred embodiments this step 1 01 includes mixing the loaded carbon with

a binder in approximately equal proportions by weight, alternatively more or less binder

may be used to accommodate the manufacturing technique and to improve even carbon

distribution. In some alternative embodiments of the invention other materials, including

iron, manganese, nickel, and/or chromium, typically in a micro powder form, are also

mixed with the carbon and binder, as a part of this step 1 01 . For the purposes of the

disclosure, carbon or carbon-like material is defined as a composition useful as a sintering

aid with tungsten, including a carbon composition, such as carbon black, graphite, nano

tubes and related carbon forms, diamond, charcoal, hydro carbon and the like and other

good sintering aid materials such as tin, bismuth, aluminum and the like.

A sintering aid is an element, compound or the like that when added to a powder to

be sintered, aids the sintering process such that some desired physical property is

attained. Sometimes a sintering aid may become a part of the final product and other

times it may vaporize off, or otherwise be eliminated, after it has acted as an aid. In some

embodiments the sintering aid may be reduced or eliminated in a pre-sinter or post-sinter

step. In some embodiments, the sintering aid is incorporated into the sintered piece. A

property commonly attained with a sintering aid is higher density achieved with lower

processing (sintering) temperatures, shorter sintering time or both. Another sometimes

desirable property is the drawing together of particles and the enhancement of

densification in all directions, to reduce or avoid slumping and distortion. This property can be achieved with lithium compounds as a sintering aid. Another sometimes desirable

properties are the maintenance of a designed shape of the final product through

production, along with densification at lower sintering temperatures and shorter firing

times. These properties can be achieved with the addition of carbon as a sintering aid.

Reactive sintering can be employed in this invention. Reactive sintering is a method

of sintering whereby some or all of the components chemically react, thereby resulting in a

sintered product that has improvements or enhancements. An example of this reactive

sintering is the carbon/FeW reaction, in which the carbon reacts with the FeW alloy and

becomes a part of the final product during sintering. It is presently believed by the

inventor, that this reaction contributes to the densification of the product at lower

temperatures and with shorter firing times, that is, the reactive sintering acts also as a

sintering aid. When the reaction of carbon with oxides of FeW occurs, there is some

reactive sintering along with the chemical reaction that occurs. In one reaction, the carbon

reacts with the oxygen that is combined with the FeW and thereby producing a carbon

monoxide and/or carbon dioxide gas, while the excess carbon reacts with the FeW that has

been left behind. The reactions in this example occur almost simultaneously, thereby likely

enhancing both the reaction sintering and sintering aid effects. A combination of these

effects is likely to occur in this invention whether the starting material is ferroalloy or

oxidized ferroalloy.

The reactive sintering, which can but need not always be used in this invention, is

different from melting or liquid phase formation in a sintering step. Often a liquid or

slushy phase may be formed during sintering, that may or may not aid the sintering step. Sometimes there is merely slumping that does not necessarily densify, and does not tend

to hold the shape of the part being sintered. In most sintering operations it is desirable to

hold the shape of the product, although substantial shrinkage often accompanies firing and

densification. If the molten phase assists densification like a sintering aid by causing

densification in all dimensions equally without slumping or distortion of the original shape,

then the molten phase itself can be considered a sintering aid.

With regard to sectional density, it is known that typically the sectional density of

round objects changes with the diameter of the object as a function of object volume.

Round shotshell shot has a sectional density that decreases with decreasing size of the

shot. Accordingly, for example, if #2 shot and #6 shot are fired from the same gun at the

same initial velocity, the #6 shot will slow down faster than the #2 shot. This difference

can be important for accurate firing at long ranges. This invention can make different

densities of shot and can therefore be used to maintain consistent density regardless of

shot size and can therefore minimize or eliminate the differences in deceleration of

different shot sizes. This advantage can have particular importance when loading different

sizes of shot in the same shotshell, because with this invention, despite the differences in

size, all the shot pellets will travel at the same speed and the pattern will tend to stay

together. As the pattern stays together, the long range effectiveness is improved.

Alternatively, in some commercial loadings, two or more different sizes of shot are used

specifically to cause the pattern to "string", that is, to lengthen out as it travels from the

bore with the larger shot leading to the small shot. In some dual shot size loads, the larger

shot is placed behind the small shot and may cause the larger shot to push through the smaller and disrupt the shot pattern. While pattern disruption or "stringing" of the pattern

may be the objective in this type of load, with the density control of this invention this

disruption or "stringing" can be minimized or enhanced in a controlled manner according

to the shot pattern characteristics desired.

Presently, the preferred form of carbon is in the form of graphite powder, although

alternative carbon sources or in some cases tin (Sn) can be substituted for the graphite in

the mixture. The present binder is a binding composition such as Acrawax, Polyvinyl

Alcohol (PVA), Paraffin or the like, although alternative binders as previously described can

be substituted without departing from the concept of this invention. FeW is added 1 02 to

the mixture of carbon and binder, presently in proportions of approximately 97% by weight

FeW; 1 .5% by weight of carbon and 1 .5% by weight of binder. In alternative embodiments

the iron in the FeW composition is replaced with one or more of Nickel; Manganese; Cobalt;

Copper; Silver; Gold; Gallium; Germanium; Chromium; Vanadium; Nickel, Niobium;

Molybdenum and the like, although generally not in sufficient quantities so as to lower the

density of the final product. Currently, the FeW is provided in a mesh-200 powder form, or

with an average particle size of 10 microns, with about 20% of the particles being

substantially larger. Although FeW is typically provided in mesh sizes of 2" by down, 3/4"

by down, 1 /4" by down or in a range, such as minus 2" plus 1 " or minus 3/4" plus 1 /4", the

FeW is presently brought down to the desired size through the use of attrition mills, ball

mills, jet mills, jaw crushers, hammer mills or any other customary technique for reducing

the size of a material. After being reduced in size, a variety of techniques, including

screens, gas classifiers and the like, can be used to assure that the corrector optimum size distribution is achieved. Blending can be used as necessary to achieve the desired average

particle size. An alternative technique for reducing the size of the FeW, or similar material,

is to oxidize the material in an appropriate furnace so that it changes form and is more

easily attritted, ball milled, jet milled or other wise reduced in average particle size. This

oxidation process provides partially or completely oxidized FeW1 which can then be

classified for blending or mixing to the appropriate proportions. Moreover, this oxidized

FeW, or other material, can also then be formed into a desired shape or loaded into a mold

that will provide the desired shape after having been mixed with an appropriate amount of

carbon and then fired in a hydrogen furnace. In such a furnace, the carbon and the

hydrogen will then reduce the FeW oxide, and facilitate the sintering to the desired density.

Since oxides have a larger volume than the FeW, or other substituted materials, there will

be greater composition shrinkage, a characteristic that can be used to reach a desired

density. The combination of carbon/binder and FeW is mixed 103 to an approximately

uniform mixture. The resulting mixture is pelletized 104, presently using standard

peptization techniques well known in the art. In alternative embodiments, rather than

pellitizing, the resulting mixture is poured into a mold to be molded, pressed or

compacted into the desired shape and/or is extruded. The pelletizing technique presently

used in this invention involves mixing the powders (typically FeW and carbon-like

materials) with a binder material, and then processing the mixed material in a machine for

rolling, tumbling or the like in order to cause the powders to adhere to each other and to

grow into spheres, pellets, rods and the like. This process is also used to homogenize

powder mixes. A wide variety of pellet sizes are possible using this pelletizing technique. This preferred pelletizing technique uses no compaction or pressure to form the pellets;

rather it is similar to rolling a snowball until it is large enough to make a snowman.

In the molding alternative, the molding is accomplished by mixing the FeW powder

and the Carbon-like material (typically graphite) and then pouring the resulting mixture

into a mold of the desired shape for firing. The mixture in its mold is then fired. This

firing of the mixture can be accomplished with one or more steps as necessary to achieve

the desired result. For example, "green" material can be fired at just enough time and

temperature to strengthen it sufficiently so that it can be further shaped before final firing,

typically without the mold. This final firing stage may be done in the tungsten powder or

in SiC grit or in graphite. The designation of SiC is not intended to indicate any particular

proportion of the composition, nor is the designation of graphite intended to limit the

forms of carbon.

The pressure or compaction alternative technique involves pressing or compacting

the mixed powder (typically FeW and graphite, usually with a binder) in a die to form the

desired shape, that is a product such as round pellets, bullets, milling media and the like.

The green ("unfired") pressing or compacted product is then typically fired, similar to the

molded product, to either a complete or an intermediate stage, where further shaping can

be accomplished with a stronger partially fired pellet, bullet or the like.

The extruded technique is another method of forming or making pellets, bullets

and bullet cores, rods, milling media and the like. Mixed powders, with or without a

binder, are forced through a die, which can be shaped and sized to give the desired cross

section, and can be of nearly any desired length. When the desired length is reached the extrusion is sheared off and is processed further to shape the product into the desired

shape. Again, the firing steps can include one or more firings as desired to further work or

shape the product prior to final firing. The extrusion die can have a single or multiple

openings. Extrusion, although not previously used in the manufacture of shotgun pellets

or bullets, is well known in the production of products from ceramics to metals, to plastics

and to foods. When extrusion is used to make the bullet cores, typically a follow on step of

"swaging" is preformed to finalize the shape and dimensions of the bullet, and/or to add a

jacket to the core. In this invention, the extrusion technique will typically be used on a

FeW, graphite and binder mixture. The extruded product may be rolled or shaped after

shearing to specific desired lengths to complete the shaping of the pellet to the desired

shape.

A Silicon-Carbide (SiC) composition is mixed 105 into the pellitized product to

more evenly distribute the heat that is applied in the following steps. As an alternative, the

SiC composition mixing step 105 can be substituted with step of mixing in tungsten

powder, ferro-tungsten powder, tungsten-carbide powder or ferro niobium powder during

sintering. Heat of approximately 6000C is applied 106 to the pelletized (or molded)

mixture for about fifteen minutes to drive out the binder, if such binder is present. In

some alternative embodiments, the choice of binder or the lack of a binder may make this

step unnecessary. An application of additional heat of approximately, in one embodiment

of 1 1 5O0C for approximately fifteen minutes is applied 107 to sinter the entire product into

the pelletized form. These heating steps 1 06, 107, can include, in some embodiments,

heating in a protective or reducing atmosphere. In the present embodiment it is desirable the temperature is maintained at or below 1 2000C1 because such lower temperatures

dramatically reduce the production cost. Also, by sintering at a temperature at or below

1 2000C high densities with a smooth finish and little or no porosity may be achieved. The

inventor has found that the addition of Mn or Ni with Carbon will enable the lowering of the

sintering temperature to below 12000C, may reduce the tendency of the resulting product

to rust, but may also lower the resulting density to about 1 0.4 g/cc. However, the addition

of both Mn and Ni combined with lowering the sintering temperature to about 1 1000C has

been shown to retain magnetic properties of the product and to maintain densities in the

1 1 .7 to 1 2.2 g/cc range. The sintering with carbon, presently in a graphite form, is used

instead of melting because the pellet is first made and then is hardened, while melting

requires higher processing temperatures and accordingly a high resulting manufacturing

cost. In an alternative embodiment, tungsten powder, tungsten carbide, manganese nickel,

ferro niobium and/or silicon carbide is added 108 as part of the sintering step 107 and

thereafter sintered to reduce the likelihood of the final material to stick to itself. In some

embodiments of this invention, this sintering step 107 is enhanced with small quantities of

manganese. This sintering in of tungsten or tungsten carbide powder further increases the

density of the resulting material and permits the alteration of the surface characteristics of

the resulting material, as well as improving the heat distribution during sintering.

Relatively large tungsten, tungsten carbide, ferro niobium or silicon carbide particle sizes

are preferred for the added 1 08 powder because of the improved heat distribution

characteristics of larger particles. For example, one present embodiment of the produced

material is provided with a dimpled surface. In another embodiment of this invention, the sintering step also includes the sintering in of SiC powder in a relatively large mesh size. In

alternative embodiments, both the temperatures, compositions and heating times are

modified to produce product with different densities, strength, toughness or friability, or

when alternative substitute materials are used. For example, if Sn is used instead of

carbon, a sintering temperature of about 10500C to 1 2000C is appropriate. In this tin

alternative, it is preferred to add tin prior to sintering and again when molten during

sintering. Tin (Sn) or tin alloys can also be added after sintering to fill voids and increase

density and to provide corrosion protection. After cooling, the resulting product is a pellet

composed of a composition of matter consisting essentially of iron-carbide-tungsten

(FexCyWz), or in alternative embodiments, iron-tungsten-tin (FexWySnz) or iron-carbide-

tungsten-tin (FewCχWySnz).

In some alternative embodiments the sintering 107 includes a pre-sinter step

followed by some machining (which may include grinding, drilling, rounding etc.) followed

by a final sinter step to finalize the formation of the product. Also, in some alternative

embodiments, the porosity as well as the density of the resulting product may be

controlled through the addition 1 09, typically after the sintering step 1 07 with possible

heat treating, of an additional material. Materials such as metals, plastics and the like, can

be used to increase or decrease the final density of the product. Tin or other corrosion

resistant metals, plastics, paints and the like can be added to increase corrosion resistance.

Ductile materials, like teflon, can also be added to cushion or reduce the surface hardness

of the final product. In some embodiments of this invention, after sintering 107 color is

added to provide a technique of identifying the shot, for example #4 is blue, #6 is red, etc., or color can be used to correspond to a weight, density, shape or size. A variety of surface

coatings can also be added to make a slick, sticky or rough surface as desired. In some

embodiments, a variety of additional materials, selected from the above may be combined

in this 109 step to create a desired combination effect or use where a non-toxic material

can be useful or required.

As noted above, in alternative embodiments, where it is desirable to retain the

magnetic properties of the resulting pellet(s) the firing (sintering) temperature is lowered

from typically about 1200 degrees C to about 1 100 degrees C and the firing time can be

reduced by about 1 5 minutes. The lower temperature and/or reduced firing time can

provide sintering without a complete reaction of the MnNi (which individually were typically

added during the mixing step 103, although alternative could have been added during the

mix with SiC step 105) with the FeW. In testing, the resulting pellet product retains its

magnetic properties and has a density of between 1 1 .7 and 1 2.3 g/cc.

While the invention has been described with respect to certain specific

embodiments, compositions and steps, it will be appreciated that many modifications and

changes may be made by those skilled in the art without departing from the invention. It is

intended, therefore, by the appended claims to cover all such modifications and changes as

may come within the true spirit and scope of the invention.

Claims

CLAIMSI claim:
1 . A method for manufacturing high-density materials, comprising:
(A) loading a carbon-like material;
(B) adding a tungsten composition;
(C) mixing said carbon-like material said tungsten composition to form
a tungsten-carbon-like mixture;
(D) shaping said tungsten-carbon-like mixture;
(E) mixing in a heat distribution composition;
(F) heating to drive out said binder forming a resulting mixture; and
(C) heating to sinter said resulting mixture to produce a high-density
low toxicity material.
2. A method for manufacturing high-density materials, as recited in claim 1 ,
further comprising mixing said introduced carbon-like material with a binder.
3. A method for manufacturing high-density materials, as recited in claim 1 ,
further comprising adding Mn and Ni to said tungsten composition.
4. A method for manufacturing high-density materials, as recited in claim 3,
wherein said heating is accomplished at a temperature low enough to avoid a complete reaction of the Mi and Ni with the FeW, to thereby retain magnetic properties in the
resulting product.
5. A method for manufacturing high-density materials, as recited in claim 1 ,
wherein said shaping said tungsten-carbon like material further comprises a step selected
from the group consisting of molding, pressing, compacting, pelletizing and extruding said
tungsten-carbide-like mixture.
6. A composition of matter comprising:
(A) FeW in a proportion of approximately 95%-99% by weight;
(B) Carbon in a proportion of approximately .5%- 5% by weight;
wherein said composition of said FeW and said carbon is formed into a pellet
appropriate for use as a shotgun pellet or bullet.
7. A composition of matter, as recited in claim 6, further comprising Mn and Ni
in mixture sintered without complete reaction with said FeW.
8. A composition of matter comprising:
(A) Tungsten, mixed with a material selected from the group consisting
of Nickel; Manganese; Cobalt; Copper; Silver; Gold; Gallium; Germanium; Chromium;
Vanadium; Niobium; Molybdenum and Iron; in a proportion of approximately 95%-99% by
weight; (B) Carbon in a proportion of approximately .5%- 5% by weight;
wherein said composition of said Tungsten mixture and said carbon is
formed into a pellet appropriate for use as a shotgun pellet or bullet.
9. A composition of matter comprising:
(A) FeW in a proportion of approximately 50%-99% by weight;
(B) Sn in a proportion of approximately l %-50% by weight;
wherein said composition of said FeW and said carbide is formed into a
pellet appropriate for use as a shotgun pellet or bullet.
1 0. A composition of matter comprising:
(A) FeW in a proportion of approximately 95%-99% by weight;
(B) Sn in combination with carbon in a proportion of approximately 1 %-
5% by weight;
wherein said composition of said FeW and said tin-carbide combination is
formed into a pellet appropriate for use as a shotgun pellet or bullet.
1 1 . A method of manufacturing high-density materials, as recited in claim 1 ,
wherein said carbon-like material is graphite.
1 2. A method of manufacturing high-density materials, as recited in claim 1 ,
wherein said carbon-like material is a sintering aid selected from the group consisting of tin, bismuth, aluminum, carbon black, graphite, nano tubes, diamond, charcoal and hydro
carbon.
1 3. A method of manufacturing high-density materials, as recited in claim 1 ,
wherein said tungsten composition further comprises a material selected from the group
consisting of Iron; Nickel; Manganese; Cobalt; Copper; Silver; Gold; Gallium; Germanium;
Chromium; Vanadium; Niobium; Molybdenum.
14. A method of manufacturing high-density materials, as recited in claim 2,
wherein said heating to drive out said binder further comprises heating in a protective
environment.
1 5. A method of manufacturing high-density materials, as recited in claim 1 ,
wherein said heating to sinter further comprises heating in a protective environment.
1 6. A method of manufacturing high-density materials, as recited in claim 2,
wherein said binder is selected from the group consisting of Acrawax, Polyvinyl Alcohol
(PVA), or Paraffin.
1 7. A method for manufacturing high-density non-toxic materials, comprising:
(A) loading a carbon based material;
(B) mixing said carbon-based material; (C) adding a tungsten composition to form a tungsten-carbon mixture;
(D) pelletizing said tungsten-carbon mixture;
(E) mixing in a heat distribution composition;
(F) sintering said mixture to produce a high-density low toxicity
material.
1 8 A method for manufacturing high-density non-toxic materials, as recited in
claim 1 7, further comprising adding Mn and Ni to said tungsten-carbon mixture.
19. A method for manufacturing high-density non-toxic materials, as recited in claim
1 7, wherein said heat distribution composition is selected from the group consisting of SiC,
W and WC.
20. A method for manufacturing high-density non-toxic materials, as recited in
claim 1 7, wherein said sintering is performed in a protective atmosphere.
21 . A method for manufacturing high-density non-toxic materials, as recited in
claim 1 7, further comprising adding Mn and Ni to said tungsten composition and wherein
said sintering is done at about 1 1 000C.
22. A method for manufacturing high-density non-toxic materials, as recited in
claim 1 7, wherein said produced high-density low toxicity material is a generally round
pellet.
23. A method for manufacturing high-density non-toxic materials, as recited in
claim 17, wherein said produced high-density low toxicity material is a generally round
dimpled pellet.
24. A method for manufacturing high-density non-toxic materials, as recited in
claim 1 7, wherein said carbon-based material is graphite and said sintering step sinters
said graphite to said tungsten composition.
25. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, comprising:
a particle comprising: a carbon-like material mixed with tungsten, pelletized
and sintered to form a high-density low toxicity particle.
26. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle further comprises a binder mixed
with said carbon-like material.
27. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle further comprises a material
selected from the group consisting of Nickel; Manganese; Cobalt, copper; Silver; Gold;
Gallium; Germanium; Chromium; Vanadium; Niobium, Molybdenum and Iron mixed with
said tungsten.
28. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle is rounded without compression.
29. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle is shaped using a step selected from
the group consisting of pelletizing, molding, pressing, compacting and extruding.
30. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle has a density of 1 1 .5 g/cc or
greater.
31 . A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle is produced at sintering
temperatures of about 1 25O°C or less.
32. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein after said pelletizing said pellet is provided with a
powder selected from the group consisting of tungsten powder, tungsten-carbide powder,
ferro nibium powder, ferro-tungsten and silicon-carbide powder, prior to sintering.
33. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said tungsten material further comprises FeW.
34. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle is generally spherically shaped.
35. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said particle is generally cylindrically shaped.
36. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile, as recited in claim 25, wherein said high-density low toxicity particle further
comprises a color coating a surface of said high-density low toxicity particle to designate
shot size.
37. A firearm projectile, such as a shotgun pellet, bullet or armor piercing
projectile as recited in claim 25, wherein Mn and Ni are used to retain magnetic properties
of said projectile.
38. A composition having high density and low toxicity, comprising:
a portion of FeW sintered to a portion of Ni and to a portion of Mn forming a
high density low toxicity composition, wherein said FeW portion is about four times the
percentage by weight than that of the percentage by weight of said portion of Ni and
wherein said FeW is about twice the percentage by weight of the Mn portion.
39. A composition, as recited in claim 38, further comprising an additional
component selected from the group consisting of Cu, Zn.
40. A composition, as recited in claim 38, wherein said sintered composition has
its density varied by addition of a material selected from the group consisting of Cu, Zn, Ni
and Mn.
41 . A composition having high density and low toxicity, comprising FeW and
which is magnetic.
42. A composition, as recited in claim 41 , wherein said composition further
comprises a coating of magnetic material.
43. A composition, as recited in claim 42, wherein said coating of magnetic
material is selected from the group consisting of Bi and Mn.
44. A composition, as recited in claim 41 , wherein said composition is sintered
in an atmosphere selected from the group consisting of Ar, N2, He and H.
45. A composition, as recited in claim 41 , wherein said FeW is composed of
particles of varying size.
46. A composition, as recited in claim 41 , further comprising the addition of a
magnetic material selected from the group consisting of Cu, Mn, Al, Fe, Ni, C, Ni, Sn, Zn.
47. A method, as recited in claim 1 7, further comprising selecting the hardness
of said produced high-density low toxicity material by adjusting the temperature of said
sintering step.
48. A method, as recited in claim 1 7, further comprising selecting the hardness
of said produced high-density low toxicity material by adding an additional composition to
said mixing step.
49. A method, as recited in claim 1 7, further comprising selecting the hardness
of said produced high-density low toxicity material by adjusting the time of said sintering
step.
50. A method, as recited in claim 1 7, wherein said pelletizing step further
comprises adding a tungsten powder to said pelletized mixture.
PCT/US2006/002826 2005-01-28 2006-01-26 Method for making a non-toxic dense material WO2007086852A3 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11046319 US20100034686A1 (en) 2005-01-28 2005-01-28 Method for making a non-toxic dense material
US11/046,319 2005-01-28

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20060849676 EP1850988A2 (en) 2005-01-28 2006-01-26 Method for making a non-toxic dense material
CA 2598122 CA2598122A1 (en) 2005-01-28 2006-01-26 Method for making dense material
AU2006336442A AU2006336442B2 (en) 2005-01-28 2006-01-26 Method for making a non-toxic dense material

Publications (2)

Publication Number Publication Date
WO2007086852A2 true true WO2007086852A2 (en) 2007-08-02
WO2007086852A3 true WO2007086852A3 (en) 2007-12-27

Family

ID=38309633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/002826 WO2007086852A3 (en) 2005-01-28 2006-01-26 Method for making a non-toxic dense material

Country Status (4)

Country Link
US (1) US20100034686A1 (en)
EP (1) EP1850988A2 (en)
CA (1) CA2598122A1 (en)
WO (1) WO2007086852A3 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8028626B2 (en) 2010-01-06 2011-10-04 Ervin Industries, Inc. Frangible, ceramic-metal composite objects and methods of making the same
US20120279412A1 (en) * 2010-01-06 2012-11-08 Ervin Industries, Inc. Frangible, ceramic-metal composite objects and methods of making the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090252637A1 (en) * 2007-12-03 2009-10-08 Energy & Environmental Research Center Foundation Joining of difficult-to-weld materials and sintering of powders using a low-temperature vaporization material
CN103471890B (en) * 2013-09-16 2015-05-13 中国科学院上海硅酸盐研究所 Pretreatment method for silicon carbide powder sample to be tested by using laser ablation inductively coupled plasma mass spectrometry
US10082374B2 (en) * 2014-08-01 2018-09-25 James Nicholas Marshall Magnetic ammunition for air guns and biodegradable magnetic ammunition for airguns

Family Cites Families (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1847617A (en) * 1928-02-11 1932-03-01 Hirsch Kupfer & Messingwerke Hard alloy
US2119876A (en) * 1936-12-24 1938-06-07 Remington Arms Co Inc Shot
US2183359A (en) * 1938-06-24 1939-12-12 Gen Electric Co Ltd Method of manufacture of heavy metallic material
US3372021A (en) * 1964-06-19 1968-03-05 Union Carbide Corp Tungsten addition agent
US3623849A (en) * 1969-08-25 1971-11-30 Int Nickel Co Sintered refractory articles of manufacture
US3900317A (en) * 1973-03-06 1975-08-19 Canadian Patents Dev Fe-sn-cu-pb sintered composite metal article and process
US3987730A (en) * 1973-03-06 1976-10-26 Canadian Patents And Development Limited Iron and lead-containing composite metal shot
DE2320399A1 (en) * 1973-04-21 1974-10-31 Rheinmetall Gmbh rifle cartridge
US4027594A (en) * 1976-06-21 1977-06-07 Olin Corporation Disintegrating lead shot
US4297133A (en) * 1976-07-15 1981-10-27 Yoshida Iron Works Co., Ltd. Method and means for adding treating agent for molten metal
US4200456A (en) * 1976-07-15 1980-04-29 Yoshida Iron Works Co. Ltd Method of and member for adding treating agent for molten metal
US4292877A (en) * 1976-10-21 1981-10-06 Lee Richard J Ammunition loader with improved charge bar
US4316414A (en) * 1979-11-09 1982-02-23 Dayron Corporation Fuze
US4784690A (en) * 1985-10-11 1988-11-15 Gte Products Corporation Low density tungsten alloy article and method for producing same
US4714023A (en) * 1986-03-27 1987-12-22 Brown John E Non-toxic shot
US4754684A (en) * 1987-04-10 1988-07-05 Enrique Borgheresi Shotgun shell shortener and method
FR2622209B1 (en) * 1987-10-23 1990-01-26 Cime Bocuze Heavy alloys of tungsten-nickel-iron having very high mechanical characteristics and method of manufacturing said alloy
US4856408A (en) * 1988-08-04 1989-08-15 Hendrickson Walter R Shot and powder loading system
US4841866A (en) * 1989-02-02 1989-06-27 Miesner Delbert W Tracer shotgun shell
US5078054A (en) * 1989-03-14 1992-01-07 Olin Corporation Frangible projectile
US4949644A (en) * 1989-06-23 1990-08-21 Brown John E Non-toxic shot and shot shell containing same
US5198616A (en) * 1990-09-28 1993-03-30 Bei Electronics, Inc. Frangible armor piercing incendiary projectile
US5603073A (en) * 1991-04-16 1997-02-11 Southwest Research Institute Heavy alloy based on tungsten-nickel-manganese
GB2257985A (en) * 1991-07-26 1993-01-27 London Scandinavian Metall Metal matrix alloys.
US5279787A (en) * 1992-04-29 1994-01-18 Oltrogge Victor C High density projectile and method of making same from a mixture of low density and high density metal powders
US5713981A (en) * 1992-05-05 1998-02-03 Teledyne Industries, Inc. Composite shot
US5831188A (en) * 1992-05-05 1998-11-03 Teledyne Industries, Inc. Composite shots and methods of making
DE69313253D1 (en) * 1992-11-27 1997-09-25 Toyota Motor Co Ltd of the same iron alloy powder for sintering, sintered iron alloy having output resistance and process for producing
GB9308287D0 (en) * 1993-04-22 1993-06-09 Epron Ind Ltd Low toxicity shot pellets
JP3258765B2 (en) * 1993-06-02 2002-02-18 川崎製鉄株式会社 Method of producing a high strength iron-based sintered body
US5913256A (en) * 1993-07-06 1999-06-15 Lockheed Martin Energy Systems, Inc. Non-lead environmentally safe projectiles and explosive container
US5335578A (en) * 1993-07-13 1994-08-09 Lorden Paul R Automatic shell feeding attachment for a reloading machine
US6158351A (en) * 1993-09-23 2000-12-12 Olin Corporation Ferromagnetic bullet
US5399187A (en) * 1993-09-23 1995-03-21 Olin Corporation Lead-free bullett
WO1996001407A1 (en) * 1994-07-06 1996-01-18 Lockheed Martin Energy Systems, Inc. Non-lead, environmentally safe projectiles and method of making same
US5527376A (en) * 1994-10-18 1996-06-18 Teledyne Industries, Inc. Composite shot
US5714573A (en) * 1995-01-19 1998-02-03 Cargill, Incorporated Impact modified melt-stable lactide polymer compositions and processes for manufacture thereof
US5623118A (en) * 1996-03-01 1997-04-22 Windjammer Tournament Wads, Inc. Shot shell wad
US5754937A (en) * 1996-05-15 1998-05-19 Stackpole Limited Hi-density forming process
US6536352B1 (en) * 1996-07-11 2003-03-25 Delta Frangible Ammunition, Llc Lead-free frangible bullets and process for making same
US5932828A (en) * 1996-12-02 1999-08-03 Hornady Manufacturing Company Reloader with snap-in tools and quick release shell or shot shell holders
JPH10226855A (en) * 1996-12-11 1998-08-25 Nippon Piston Ring Co Ltd Valve seat for internal combustion engine made of wear resistant sintered alloy
US6209180B1 (en) * 1997-03-25 2001-04-03 Teledyne Industries Non-toxic high density shot for shotshells
GB2325005B (en) * 1997-05-08 2000-10-11 Brico Eng Method of forming a component
US5861572A (en) * 1997-06-02 1999-01-19 Alltrista Corporation Universal shotgun shell wad
US5874689A (en) * 1997-06-02 1999-02-23 Federal Cartridge Company Shot pouch
US5997805A (en) * 1997-06-19 1999-12-07 Stackpole Limited High carbon, high density forming
JPH1137232A (en) * 1997-07-24 1999-02-12 Honda Motor Co Ltd Automatic tensioner
US5905936A (en) * 1997-08-06 1999-05-18 Teledyne Wah Chang Method and apparatus for shaping spheres and process for sintering
DE19748343C2 (en) * 1997-11-03 2001-11-22 Danfoss As hydraulic valve
US5970878A (en) * 1997-12-15 1999-10-26 Olin Corporation Universal shot wad
US6016754A (en) * 1997-12-18 2000-01-25 Olin Corporation Lead-free tin projectile
US6092467A (en) * 1998-01-27 2000-07-25 Skyblazer, Inc. Flare apparatus
JP3249469B2 (en) * 1998-05-12 2002-01-21 漢俊 金 Tongue cleaning tool
US6112669A (en) * 1998-06-05 2000-09-05 Olin Corporation Projectiles made from tungsten and iron
US6128846A (en) * 1998-06-08 2000-10-10 Inpromark, Inc. Length shotgun choke tube
US6270549B1 (en) * 1998-09-04 2001-08-07 Darryl Dean Amick Ductile, high-density, non-toxic shot and other articles and method for producing same
US6527880B2 (en) * 1998-09-04 2003-03-04 Darryl D. Amick Ductile medium-and high-density, non-toxic shot and other articles and method for producing the same
US6263797B1 (en) * 1998-12-30 2001-07-24 Skyblazer, Inc. Enhanced flare apparatus
US6749662B2 (en) * 1999-01-29 2004-06-15 Olin Corporation Steel ballistic shot and production method
US6202561B1 (en) * 1999-06-25 2001-03-20 Federal Cartridge Company Shotshell having pellets of different densities in stratified layers
US6358298B1 (en) * 1999-07-30 2002-03-19 Quebec Metal Powders Limited Iron-graphite composite powders and sintered articles produced therefrom
US6447715B1 (en) * 2000-01-14 2002-09-10 Darryl D. Amick Methods for producing medium-density articles from high-density tungsten alloys
US6553836B2 (en) * 2000-07-21 2003-04-29 John T. Williams Surface acoustic wave (SAW) accelerometer
US6514307B2 (en) * 2000-08-31 2003-02-04 Kawasaki Steel Corporation Iron-based sintered powder metal body, manufacturing method thereof and manufacturing method of iron-based sintered component with high strength and high density
US6537489B2 (en) * 2000-11-09 2003-03-25 Höganäs Ab High density products and method for the preparation thereof
US6551375B2 (en) * 2001-03-06 2003-04-22 Kennametal Inc. Ammunition using non-toxic metals and binders
WO2002087808A3 (en) * 2001-04-26 2002-12-27 Internat Non Toxic Composites Composite material containing tungsten, tin and organic additive
WO2003033753A3 (en) * 2001-10-16 2003-07-31 Kenneth H Elliott High density non-toxic composites comprising tungsten, another metal and polymer powder
WO2003064961A1 (en) * 2002-01-30 2003-08-07 Amick Darryl D Tungsten-containing articles and methods for forming the same
US6749802B2 (en) * 2002-01-30 2004-06-15 Darryl D. Amick Pressing process for tungsten articles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8028626B2 (en) 2010-01-06 2011-10-04 Ervin Industries, Inc. Frangible, ceramic-metal composite objects and methods of making the same
US20120279412A1 (en) * 2010-01-06 2012-11-08 Ervin Industries, Inc. Frangible, ceramic-metal composite objects and methods of making the same
US8468947B2 (en) 2010-01-06 2013-06-25 Ervin Industries, Inc. Frangible, ceramic-metal composite objects and methods of making the same

Also Published As

Publication number Publication date Type
WO2007086852A3 (en) 2007-12-27 application
US20100034686A1 (en) 2010-02-11 application
EP1850988A2 (en) 2007-11-07 application
CA2598122A1 (en) 2007-08-02 application

Similar Documents

Publication Publication Date Title
US5616642A (en) Lead-free frangible ammunition
US4613370A (en) Hollow charge, or plate charge, lining and method of forming a lining
US6517774B1 (en) High density composite material
US5877437A (en) High density projectile
US4498395A (en) Powder comprising coated tungsten grains
US4383853A (en) Corrosion-resistant Fe-Cr-uranium238 pellet and method for making the same
US5279787A (en) High density projectile and method of making same from a mixture of low density and high density metal powders
US3888636A (en) High density, high ductility, high strength tungsten-nickel-iron alloy & process of making therefor
US4881465A (en) Non-toxic shot pellets for shotguns and method
US6350407B1 (en) Process for producing sintered product
US5950064A (en) Lead-free shot formed by liquid phase bonding
US7011027B2 (en) Coated metal particles to enhance oil field shaped charge performance
US5535495A (en) Die cast bullet manufacturing process
US5778301A (en) Cemented carbide
US4949644A (en) Non-toxic shot and shot shell containing same
US6355209B1 (en) Metal consolidation process applicable to functionally gradient material (FGM) compositons of tungsten, nickel, iron, and cobalt
US2409307A (en) Projectile
US4428295A (en) High density shot
US3841901A (en) Aluminum-and molybdenum-coated nickel, copper or iron core flame spray materials
US5740516A (en) Firearm bolt
US5763819A (en) Obstacle piercing frangible bullet
US5917143A (en) Frangible powdered iron projectiles
US6632263B1 (en) Sintered products having good machineability and wear characteristics
US5665808A (en) Low toxicity composite bullet and material therefor
US7232473B2 (en) Composite material containing tungsten and bronze

Legal Events

Date Code Title Description
ENP Entry into the national phase in:

Ref document number: 2598122

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2006336442

Country of ref document: AU

ENP Entry into the national phase in:

Ref document number: 2006336442

Country of ref document: AU

Date of ref document: 20060126

Kind code of ref document: A